Apparatus for reducing organic halide contamination in hydrocarbon products using a metal chloride

ABSTRACT

This application provides an apparatus for making a hydrocarbon with a reduced amount of an organic halide, comprising:
         a. a process unit comprising an effluent port, that produces and discharges the hydrocarbon comprising the organic halide; and   b. a halide removal vessel with an inlet that feeds the hydrocarbon from the process unit, wherein the halide removal vessel comprises an anhydrous metal chloride and in which the hydrocarbon comprising the organic halide is contacted with the anhydrous metal chloride under anhydrous conditions to produce a contacted hydrocarbon having from 50-100 wt % of a total halide in the hydrocarbon removed.

This application is a continuation of an earlier patent applicationtitled “METHOD FOR REDUCING ORGANIC HALIDE CONTAMINATION IN HYDROCARBONPRODUCTS USING A METAL CHLORIDE” (Publication No. US20140357915A1,application Ser. No. 13/905,282, filed on May 30, 2013); hereinincorporated in its entirety.

TECHNICAL FIELD

This application is directed to an apparatus for reducing organic halidecontamination in hydrocarbon products by contacting a hydrocarbonfraction comprising an organic halide contaminant with metal chlorideunder anhydrous conditions.

BACKGROUND

Alternative and improved methods for reducing organic halidecontaminants in hydrocarbon products produced by ionic liquid catalyzedhydrocarbon conversion reactions are desired.

SUMMARY

This application provides an apparatus for making a hydrocarbon with areduced amount of an organic halide, comprising:

-   -   a. a process unit comprising an effluent port, that produces and        discharges the hydrocarbon comprising the organic halide; and    -   b. a halide removal vessel with an inlet that feeds the        hydrocarbon from the process unit, wherein the halide removal        vessel comprises an anhydrous metal chloride and in which the        hydrocarbon comprising the organic halide is contacted with the        anhydrous metal chloride under anhydrous conditions to produce a        contacted hydrocarbon having from 50-100 wt % of a total halide        in the hydrocarbon removed.

The present invention may suitably comprise, consist of, or consistessentially of, the elements a and b, as described above.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram of a parallel arrangement of halide removal vessels.

FIG. 2 is a diagram of a series arrangement of halide removal vessels.

DETAILED DESCRIPTION

The hydrocarbon comprising the organic halide can be made in variousprocess units using different catalysts and processes. The process unitcan perform, for example, isoparaffin alkylation with olefins;oligomerization of olefins to make distillate, base oil or polymers;paraffin dis-proportionation; aromatic alkylation; aromatictrans-alkylation; acetylation; metatheses; and co-polymerization.

The term ‘anhydrous’ means that there is essentially no water present.For example, the amount of water present can be from zero to 20 wppm.

Hydrocarbon Comprising an Organic Halide

Examples of these hydrocarbons include alkylate products,oligomerization products, or mixtures thereof. In one embodiment thehydrocarbon comprising the organic halide comprises a gasoline blendingcomponent, a middle distillate, a lubricant, or a mixture thereof.Gasoline blending components can be blended into gasoline or useddirectly as gasoline. Examples of gasoline blending components arenaphtha and heavy naphtha. In the context of this disclosure, naphthahas a boiling range distribution less than 130° C. and heavy naphtha hasa boiling range distribution from 130 to 200° C. In one embodiment, thegasoline blending component has a high octane number. In thisembodiment, the gasoline blending component can have a RON from 80-105.Examples of high octane numbers are 82 or higher, 85 or higher, 90 orhigher, and 95 or higher. Different methods are used for calculatingoctane numbers of fuels or fuel blend components. The Research-methodoctane number (RON) is determined using ASTM D 2699-07a. The test formeasuring RON employs the standard Cooperative Fuel Research (CFR)knock-test engine. Additionally, the Research-method octane number canbe calculated [RON (GC)] from gas chromatography boiling rangedistribution data. The RON (GC) calculation is described in thepublication, Anderson, P. C., Sharkey, J. M., and Walsh, R. P., “JournalInstitute of Petroleum”, 58 (560), 83 (1972).

A “middle distillate” is a hydrocarbon product having a boiling rangebetween 250 to 735° F. (121° to 391° C.). The term “middle distillate”includes the diesel, heating oil, jet fuel, and kerosene boiling rangefractions. It can also include a portion of naphtha or light oil. In thecontext of this disclosure, a “base oil” is a hydrocarbon boiling in therange of about 650° F. (343 degree Celsius) and higher. Base oils can beblended with additives and used, for example, as diluents for theadditives or in finished lubricants.

The test methods used for boiling range distributions of thehydrocarbons in this disclosure are ASTM D 2887-06a and ASTM D 6352-04.The boiling range distribution determination by distillation can besimulated by the use of gas chromatography. The boiling rangedistributions obtained by gas chromatography are essentially equivalentto those obtained by true boiling point (TBP) distillation (see ASTMTest Method D 2892), but are not equivalent to results from lowefficiency distillations such as those obtained with ASTM Test Methods D86 or D 1160.

In one embodiment, the hydrocarbon is an alkylate gasoline blendingcomponent that has a RON that is from 0 to 1.0 different from acontacted RON of the contacted hydrocarbon. In this embodiment, thecontacting with the metal chloride does not degrade the quality of thealkylate gasoline blending component.

In one embodiment the hydrocarbon is saturated, with no double bonds. Inanother embodiment, the hydrocarbon and the contacted hydrocarbon aresaturated. In another embodiment, the hydrocarbon, the contactedhydrocarbon, or both can be unsaturated. Examples of saturatedhydrocarbons include C2-C60 hydrocarbons, such as n-butane, n-pentane,and trimethylpentane.

In one embodiment, the hydrocarbon comprising the organic halide can beproduced in a process unit comprising an ionic liquid catalystcomprising an anhydrous metal chloride.

Process Unit

The process unit can be any set of equipment or a reactor that is usedto produce the hydrocarbon comprising the organic halide. The processunit is designed to handle the hydrocarbon feeds, to perform the desiredcatalytic function on the feeds, as well as to discharge the hydrocarboncomprising the organic halide. It can have reactor inlet ports, areactor chamber, and effluent ports. In one embodiment, the process unitadditionally comprises an alkyl halide or a hydrogen halide. Alkylhalides and hydrogen halides can be used as promoters for the ionicliquid or other acid catalyst. Examples of processes using anhydrous HClare described in co-owned U.S. Pat. No. 7,432,408. Examples of processesusing alkyl halide promoters are described in co-owned U.S. Pat. Nos.7,495,144 and 7,531,707. In one embodiment, the alkyl halide comprises aC2-C10, or a C2-C6, alkyl halide. When alkyl halide is used as apromoter, HCl can be formed in situ in the process unit. In oneembodiment, the alkyl halide comprises a C2-C6 alkyl halide.

Ionic Liquid Catalyst

Ionic liquids are generally organic salts with melting points below 100°C., and often below room temperature. They can find applications invarious chemical reactions, solvent processes, and electrochemistry.Ionic liquid catalysts can be used for a wide variety of chemicalreactions, including alkylation, dimerization, oligomerization,acetylation, metatheses, and co-polymerization. The ionic liquidcatalyst of this invention comprises an anhydrous metal chloride.Examples of anhydrous metal chlorides that can be used include AlCl₃,TiCl₄, SnCl₄, and FeCl₃. Anhydrous metal chlorides are used because theionic liquid catalysts comprising the anhydrous metal chlorides arehighly water reactive and can be dangerous to use when water is present.

Most ionic liquids are prepared from organic cations and inorganic ororganic anions. Cations include, but are not limited to, ammonium,phosphonium and sulphonium. Anions include, but are not limited to:BF₄—, PF₆—, haloaluminates such as Al₂Cl₂—, Al₃Cl₁₀—, and Al₂Br₇—,[(CF₃SO₂)2N]—, alkyl sulfates (RSO₃—), and carboxylates (RCO₂—).

In one embodiment, the ionic liquid catalyst comprising an anhydrousmetal chloride is chloroaluminate ionic liquid catalyst. The use ofchloroaluminate ionic liquids as alkylation catalysts in petroleumrefining has been described, for example, in commonly assigned U.S. Pat.Nos. 7,531,707, 7,569,740, and 7,732,654.

In one embodiment, the ionic liquid catalyst is a quaternary ammoniumchloroaluminate ionic liquid salt. Examples of quaternary ammoniumchloroaluminate ionic liquid salts are an N-alkyl-pyridiniumchloroaluminate, an N-alkyl-alkylpyridinium chloroaluminate, apyridinium hydrogen chloroaluminate, an alkyl pyridinium hydrogenchloroaluminate, a di-alkyl-imidazolium chloroaluminate, atetra-alkyl-ammonium chloroaluminate, a tri-alkyl-ammonium hydrogenchloroaluminate, or a mixture thereof.

For example, a typical reaction mixture to prepare n-butyl pyridiniumchloroaluminate ionic liquid salt is shown below:

Metal Chloride

The hydrocarbon comprising the organic halide is contacted with a metalchloride. The metal chloride can be the same or different from theanhydrous metal chloride that is in the ionic liquid catalyst used inthe process unit to produce the hydrocarbon. The metal chloride can beany chloride salt of alkaline earth metals or transition metals inGroups 1, 2, and 4-12 of the IUPAC Periodic Table of the Elements datedJun. 1, 2012. Examples of metal chlorides that can be used comprisebarium chloride, calcium chloride, zinc chloride, magnesium chloride,iron chloride, chromium chloride, copper chloride, or a mixture thereof.

The contacting with the metal chloride produces the contactedhydrocarbon having a reduced amount of an organic halide, and from50-100 wt % of the total halide in the hydrocarbon is removed. In otherembodiments, from 70-100 wt %, from 80-100 wt %, or even from 90-100 wt% of the total halide in the hydrocarbon is removed. In one embodiment,the process for removing the organic halide is different from absorptionor adsorption. In this embodiment, the metal chloride functions as acatalyst and the efficacy for removing the total halide improves withincreasing temperature. One benefit of the metal chloride functioning asa catalyst is that the metal chloride can be used for an extended time,or continuously, without reactivation. Without being bound by theory, wesuspect the catalytic reaction can be: RCl⇄R={olefin}+HCl

The organic chloride, or other organic halide, decomposes readily in thepresence of the metal chloride (e.g., calcium chloride) under anhydrousconditions and at a temperature from 50° C. to 400° C. The contactingcan also generate significant amounts of HCl gas. In one embodiment, theHCl gas is vented. In another embodiment, the HCl gas is removed fromthe halide removal vessel using a purge gas. In yet another embodiment,the HCl gas is absorbed onto a suitable absorbent. Maintaining a lowconcentration of the HCl in the halide removal vessel facilitates thecontinued conversion of RCl to R═.

In one embodiment, the halide removal vessel comprises both a metalchloride and a metal oxide. The metal oxide can be present on anabsorbent used to remove chloride, for example. Metal oxides areeffective for decomposing organic chlorides at elevated temperature byabsorbing HCl produced by the decomposition reaction. As the metal oxideabsorbs the HCl, some of the metal oxide is converted to metal chloridein the halide removal vessel and the metal chloride becomes active forcontacting the hydrocarbon to further reduce the organic halide in thehydrocarbon.

Organic Halide

The organic halide in the hydrocarbon can be present in an amount thatis substantial and undesirable. Organic halide can contribute tocorrosion of equipment, and can form unwanted byproducts duringsubsequent use or combustion. In different embodiments, the total halidein the hydrocarbon is from 20 to 100 wppm, 50 to 5,000 wppm, 100 to4,000 wppm, or 75 to 2,500 wppm. In one embodiment, the organic halidein the hydrocarbon product is an organic chloride. The organic chloridemay comprise one or more alkyl chlorides, e.g., a C2-C60 alkyl chloride.In one embodiment, the organic chloride comprises a C4-C16 organicchloride.

Separating

In one embodiment, the hydrocarbon is separated from an ionic liquidcatalyst prior to contacting the hydrocarbon with the metal chloride.Any separator that effectively does this can be used. Examples ofseparators include coalescers, decanters, centrifuges, separatingcolumns, and filters. Examples of effective coalescing separators thatcan be used are described in co-owned U.S. Pat. No. 8,067,656.

In one embodiment, the apparatus for making a hydrocarbon with a reducedamount of an organic halide comprises:

a. a process unit, containing an ionic liquid catalyst comprising ananhydrous metal chloride, that produces the hydrocarbon comprising theorganic halide;

b. a separator that separates the hydrocarbon comprising the organichalide from the ionic liquid catalyst; and

c. a halide removal vessel, in which the hydrocarbon comprising theorganic halide that has been separated from the ionic liquid catalyst iscontacted with a metal chloride under anhydrous conditions to produce acontacted hydrocarbon having from 50-100 wt % of a total halide in thehydrocarbon removed.

In one embodiment, the halide removal vessel also contains an adsorbentor other material that selectively removes HCl, thus producing thecontacted hydrocarbon without HCl and having from 50-100 wt % of a totalhalide in the hydrocarbon removed.

Contacting

In one embodiment, the contacting of the hydrocarbon comprising theorganic halide with the metal halide is done under anhydrous conditionsin a halide removal vessel. The halide removal vessel can be a chlorideremoval vessel, for example. By anhydrous is meant that from 0 to 20, orfrom 0 to 5, wppm water is present in the halide removal vessel wherethe contacting occurs. The anhydrous conditions prevent the metal halidefrom becoming hydrolyzed into less active catalysts for organic chlorideremoval. The level of water can be controlled to higher or lower levelsdepending on the metallurgy used in the halide removal vessel.

In one embodiment, metal oxide, metal hydroxide, or metal carbonate areconverted in the presence of HCl under the anhydrous conditions in thehalide removal vessel. Examples of these materials include calciumoxide, calcium hydroxide, or calcium carbonate, which are converted tocalcium chloride in the presence of HCl under the anhydrous conditionsin the halide removal vessel. The calcium oxide, calcium hydroxide, orcalcium carbonate can be components in adsorbents comprising mixed metaloxides.

In one embodiment, the metal chloride is produced from an adsorbentcomprising a metal oxide. In one embodiment, the adsorbent comprising ametal oxide comprises from 5 to 75 wt % CaO, or 30 to 60 wt % CaO. Inone embodiment, the adsorbent comprising a metal oxide comprises bothCaO and ZnO or both CaO and MgO. The adsorbent can either be supportedor unsupported. When used, typical supports include various kinds ofcarbon, alumina, and silica. In one embodiment, the adsorbent issupported on clay. Examples of clays are montmorillonite, bentonite,kaolin, gairome, and kibushi. The activity of the adsorbent for removingchloride does not decline with the formation of the CaCl₂ in theadsorbent, indicating that CaCl₂ contributes to the removal of theorganic chloride from the hydrocarbon. The presence of the CaCl₂ in theadsorbent can extend the activity of the adsorbent comprising the metaloxide.

The conditions for the contacting can include one or more of thefollowing, a contacting temperature from 50° C. to 400° C., a liquidhourly space velocity (LHSV) from 0.5 to 20 h⁻¹, a mass ratio of thehydrocarbon to the metal chloride from 0.5 to 200, a pressure of 20 to5000 kPa, and a contact time of one to 4320 minutes (0.017 to 72 hours),or 9 to 2160 minutes (0.15 to 36 hours). In one embodiment thecontacting temperature is from 50° C. to less than 225° C. In anotherembodiment, the contacting temperature is from 100° C. to less than 225°C. In yet another embodiment, the contacting temperature is less than205° C. A liquid hourly space velocity (LHSV) from 0.5 to 20 h⁻¹ can beused in a continuous system. A mass ratio of the hydrocarbon to themetal chloride from 0.5 to 200 can be used in a batch system.

In one embodiment, the hydrocarbon is fed directly to the halide removalvessel from a treatment that heats the hydrocarbon to the contactingtemperature. An example of this is from an isostripper column, such asdescribed in U.S. Pat. No. 4,280,880, where the hydrocarbon effluentfrom the isostripper column has a contacting temperature of 275° F. (135degree Celsius) to 400° F. (204.4 degree Celsius). In this embodiment,additional heating and compression for the halide removal vessel can bereduced or entirely eliminated.

In one embodiment, the hydrocarbon comprises 50 to 5,000 wppm of thetotal chloride and the contacted hydrocarbon comprises from zero to 10wppm of the total chloride.

In another embodiment, the hydrocarbon comprises from 20 to 100 wppm ofthe total chloride and the contacted hydrocarbon comprises from zero to5 wppm of the total chloride.

The contacting can occur in two or more beds, wherein one bed can beused for the contacting while a different bed can be re-charged with themetal chloride or used in a cascading arrangement. This feature isdemonstrated in FIGS. 1 and 2. In FIG. 1, two halide removal vessels arearranged in parallel, where one is used at a time. In FIG. 2, two halideremoval vessels are arranged in a series, where one of the halideremoval vessels follows another. This series arrangement can be used toremove the organic halide contaminants in a step-wise fashion to lowerand lower levels. In one embodiment, the series arrangement of vesselscan include additional halide removal vessels, such as from three toten, to obtain the contacted hydrocarbon having a higher wt % of thetotal halide in the hydrocarbon removed. In one embodiment, thehydrocarbon passes through a freshest bed last. The freshest bed meansthat the metal chloride was most recently re-charged to that bedcompared to others being used for the contacting.

In one embodiment, the contacting occurs in two or more beds wherein onebed is used for the contacting while a different bed is re-charged withthe metal chloride or operated in standby. When ‘operated in standby’,the different bed is kept in readiness to serve as a substitute bed forcontacting, if and when it is needed.

The halide removal vessels used for the contacting are made from variousmaterials, including those that are resistant to chloride corrosion, andthose that are less resistant to chloride corrosion. Because theconditions in the halide removal vessel are anhydrous, chloridecorrosion is much less likely to occur. Steels with higher levels ofchromium, nickel, molybdenum and nitrogen increase resistance tolocalized corrosion and can be used, but are not necessary. Othermaterials that could be used include carbon steel, stainless steel,aluminum, glass, polymers, or plastics. Specific examples of steelmaterials that can be used are the HASTELLOY® corrosion resistant alloystrademarked by Haynes International, Inc. Another example of a corrosionresistant alloy that can be used is MONEL® alloy. MONEL® is a trademarkof Special Metals Corporation for a series of nickel alloys, primarilycomposed of nickel (up to 67%) and copper, with some iron and othertrace elements.

In one embodiment, the contacting occurs as a polishing step after afirst chloride removal step. The first chloride removal step could beone or more of the following: caustic wash, hydrodechlorination, anothercatalytic dechlorination, or absorption, for example.

In another embodiment, the contacting occurs before a finishing step,using a caustic wash or a bed of potassium hydroxide (KOH), to furthertreat the contacted hydrocarbon.

EXAMPLES Example 1 Ionic Liquid Catalyst Comprising Anhydrous MetalChloride

Various ionic liquid catalysts made of metal chlorides such as AlCl₃,GaCl₃, and InCl₃ could be used in the alkylation process unit.N-butylpyridinium chloroaluminate (C₅H₅NC₄H₉Al₂Cl₇) ionic liquidcatalyst is an example of a catalyst used in our alkylation processunits to make an alkylate gasoline blending component. The ionic liquidcatalyst had the following composition:

Wt % Al 12.4 Wt % Cl 56.5 Wt % C 24.6 Wt % H 3.2 Wt % N 3.3

Example 2 Alkylation of C₄ Olefin and Isobutane to Make AlkylateGasoline Blending Component in Pilot Plant

Evaluation of C₄ olefins alkylation with isobutane was performed in acontinuously stirred tank reactor using typical refinery mixed C₄ olefinfeed and isobutane. An 8:1 molar mixture of isobutane and olefin was fedto the reactor while vigorously stirring. The ionic liquid catalystdescribed in Example 1 was fed to the reactor via a second inlet porttargeting to occupy 6 vol % in the reactor. A small amount of n-butylchloride was added to produce anhydrous HCl gas. The average residencetime (combined volume of feeds and catalyst) was about 6 minutes. Theoutlet pressure was maintained at 200 psig and the reactor temperaturewas maintained at 95° F. (35° C.) using external cooling.

A sample of fully saturated alkylate gasoline blending componentproduced in the pilot plant was analyzed by X-ray fluorescence (XRF) fortotal chlorides and analyzed by GC to calculate RON and to measure thewt % trimethylpentane (wt % TMP) in C8 fraction. The results are shownbelow.

Alkylate Gasoline Blending Component Total Chlorides, wppm (XRF) 455 RON(GC) 90.7 Wt % TMP in C8 Fraction (GC) 83

Example 3 Organic Chloride Reduction at Elevated Temperature(Comparative Case)

To examine the effect of heating without a metal chloride on chlorideremoval in a hydrocarbon, a base case experiment was performed. 100 g ofthe alkylate gasoline blending component from Example 2, containing 455wppm total chlorides by XRF, was placed in a 300 mL HASTELLOY® C-276Parr autoclave. The autoclave was purged with dry nitrogen beforeheating, to ensure anhydrous conditions in the autoclave. The alkylategasoline blending component was heated to 200° C. while stirring, andthen held at that temperature for twelve hours. The alkylate gasolineblending component was cooled to room temperature, to approximately 25°C. The contacted alkylate gasoline blending component had 392 wppmchloride, which corresponded to a 14 wt % reduction in total chloridefrom the starting alkylate gasoline blending component.

Example 4 Organic Chloride Reduction with Calcium Chloride

Anhydrous calcium chloride (99%+purity) was purchased from Aldrich andused without any treating. 50 mL of the alkylate gasoline blendingcomponent from Example 2 and 5.026 g of calcium chloride were loadedinto a 300 mL HASTELLOY® C-276 Parr autoclave. The mixture of alkylategasoline blending component and calcium chloride was heated to 200° C.while stirring, and then held at that temperature for twelve hours. Theautoclave was cooled to room temperature and the contacted hydrocarbonwas filtered to obtain clean contacted alkylate gasoline blendingcomponent. The contacted alkylate gasoline blending component had 1 wppmchloride, which corresponded to 99.8 wt % reduction in total chloridefrom the starting alkylate gasoline blending component. Notably, in thisexperiment there was no adsorbent material in the autoclave and thechloride reduction was orders of magnitude higher than that obtained inthe base case shown in Example 3.

Results of Examples 3 and 4 are compared in the following table.

Tempera- Cata- ture in Total lyst Alkyl- Chloride Choride, Wt % Cata-Amount, ate, Removal wppm by Chloride RON lyst g g Vessel XRF Removed(GC) None 0 — As 455 Base 90.7 produced None 0 100 200° C. 392 14 90.7CaCl₂ 5.026 50 200° C. 1.0 99.8 90.6

The contacted alkylate gasoline blending component had a contacted RONthat was only 0.1 different from the original alkylate gasoline blendingcomponent. The contacting with the metal chloride caused no degradationof the alkylate gasoline blending component.

Example 5 Oxide Based Adsorbents/Absorbents

Various oxides of metals were prepared and/or purchased to compare theirabilities to reduce organic chloride in hydrocarbons.

These materials had the following compositions:

Fe₂O₃ Aldrich, 99+% ZnO Aldrich, 99+% CaO Prepared by Calcining CaCO₂ at850° C. MgO MgO (dried at 350° C.)

Example 6 Comparison of Calcium Chloride Vs. Oxide Based Adsorbent forOrganic Chloride Reduction

The fully saturated feed alkylate containing 455 ppm total chlorides byXRF was placed in a 300 mL HASTELLOY® C-276 Parr autoclave and contactedwith varying amounts and compositions of oxides and chlorides of metals.The autoclave was purged with dry nitrogen before heating, to ensureanhydrous conditions in the autoclave. The mixtures of the alkylate andtest materials were controlled to a contacting temperature of 200° C.,and they were stirred for twelve hours. The conditions and resultsachieved are summarized below.

Mass Ra- Chlo- Wt % RON Test Alkyl- Adsor- tio Alkyl- ride, Chlo- (GC)Mate- ate bent ate/Adsor- wppm ride After Con- rial (g) (g) bent by XRFRemoved tacting Base — 0 — 455 Base 90.7 Case Fe₂O₃ 50 5.012 10 234 48.790.7 ZnO 50 5.063 10 174 61.8 90.6 CaO 50 2.009 24.9 138 69.7 90.7 MgO50 5.013 10 0.9 99.8 90.7 CaCl₂ 50 5.026 10 1.0 99.8 90.6 MgCl₂ 50 5.00610 105 77.0 91.0

Even in the absence of an absorbent material, 14 wt % of the totalchloride was reduced by the 12 hour test.

The contacting with the metal oxides in the table above showed reductionof organic chloride in the range of 48.7-99.8 wt %. The primarymechanism for organic chloride reduction by contacting with metal oxideswas high temperature decomposition followed by adsorption of HCl.

As shown in Example 4, and in the above table, the CaCl₂ removed 99.8 wt% of the total chloride in the alkylate gasoline blending component by acatalytic process. The chloride removal by the CaCl₂ in the alkylategasoline blending component was as good as or better than the chlorideremoval by any other commercial adsorbents that were tested. Thecontacting with the MgCl₂ gave greater than 75 wt % of the total halidein the hydrocarbon removed, and provided a contacted RON that was higherthan the RON of the hydrocarbon before contacting.

The transitional term “comprising”, which is synonymous with“including,” “containing,” or “characterized by,” is inclusive oropen-ended and does not exclude additional, unrecited elements or methodsteps. The transitional phrase “consisting of” excludes any element,step, or ingredient not specified in the claim. The transitional phrase“consisting essentially of” limits the scope of a claim to the specifiedmaterials or steps “and those that do not materially affect the basicand novel characteristic(s)” of the claimed invention.

For the purposes of this specification and appended claims, unlessotherwise indicated, all numbers expressing quantities, percentages orproportions, and other numerical values used in the specification andclaims, are to be understood as being modified in all instances by theterm “about.” Furthermore, all ranges disclosed herein are inclusive ofthe endpoints and are independently combinable. Whenever a numericalrange with a lower limit and an upper limit are disclosed, any numberfalling within the range is also specifically disclosed.

Any term, abbreviation or shorthand not defined is understood to havethe ordinary meaning used by a person skilled in the art at the time theapplication is filed. The singular forms “a,” “an,” and “the,” includeplural references unless expressly and unequivocally limited to oneinstance.

All of the publications, patents and patent applications cited in thisapplication are herein incorporated by reference in their entirety tothe same extent as if the disclosure of each individual publication,patent application or patent was specifically and individually indicatedto be incorporated by reference in its entirety.

This written description uses examples to disclose the invention,including the best mode, and also to enable any person skilled in theart to make and use the invention. Many modifications of the exemplaryembodiments of the invention disclosed above will readily occur to thoseskilled in the art. Accordingly, the invention is to be construed asincluding all structure and methods that fall within the scope of theappended claims. Unless otherwise specified, the recitation of a genusof elements, materials or other components, from which an individualcomponent or mixture of components can be selected, is intended toinclude all possible sub-generic combinations of the listed componentsand mixtures thereof.

The invention illustratively disclosed herein suitably may be practicedin the absence of any element which is not specifically disclosedherein.

It is claimed:
 1. An apparatus for making a hydrocarbon with a reducedamount of an organic halide, comprising: a. a process unit comprising aneffluent port, that produces and discharges the hydrocarbon comprisingthe organic halide; and b. a halide removal vessel with an inlet thatfeeds the hydrocarbon from the process unit, wherein the halide removalvessel comprises an anhydrous metal chloride and in which thehydrocarbon comprising the organic halide is contacted with theanhydrous metal chloride under anhydrous conditions to produce acontacted hydrocarbon having from 50-100 wt % of a total halide in thehydrocarbon removed.
 2. The apparatus of claim 1, wherein the processunit comprises an ionic liquid catalyst.
 3. The apparatus of claim 2,wherein the process unit additionally comprises an alkyl halide.
 4. Theapparatus of claim 2, wherein the ionic liquid catalyst is achloroaluminate ionic liquid catalyst.
 5. The apparatus of claim 1,wherein the anhydrous metal chloride comprises a calcium chloride, amagnesium chloride, an iron chloride, a chromium chloride, a zincchloride, a copper chloride, or a mixture thereof.
 6. The apparatus ofclaim 1, wherein the halide removal vessel comprises two or more bedsarranged in parallel, where one bed is used at a time.
 7. The apparatusof claim 1, wherein the halide removal vessel comprises two or more bedsarranged in parallel, wherein one bed is used for the contacting whileanother bed is operated in standby or is being re-charged with theanhydrous metal chloride.
 8. The apparatus of claim 1, wherein thehalide removal vessel comprises two or more beds arranged in series. 9.The apparatus of claim 1, wherein the halide removal vessel additionallycomprises a metal oxide.
 10. The apparatus of claim 1, wherein thehalide removal vessel additionally comprises a material that selectivelyremoves HCl and produces the contacted hydrocarbon without the HCl. 11.The apparatus of claim 1, wherein the anhydrous metal chloride comprisescalcium chloride and the contacted hydrocarbon has from 90-100 wt % ofthe total halide in the hydrocarbon removed.
 12. The apparatus of claim1, wherein the anhydrous metal chloride has from 0 to 10 wppm water. 13.The apparatus of claim 1, wherein the hydrocarbon is an alkylategasoline blending component, wherein the anhydrous metal chloridecomprises a magnesium chloride, and wherein the contacting provides acontacted RON that is higher than a RON of the alkylate gasolineblending component before the contacting and removes greater than 75 wt% of the total halide.